Anthraquinone dyes and process of making them.



MAX HENRY ISLER AND oscim 'BALLY, or 'MANNHE-IM, GERMANY, asst-mes "To" BADISCHE ANILIN & SODA FABRIK, or LUowmsHAr-EN-oN-mmnmn' Gang.

MANY, A CORPORATION.

ANTHRAQUINONE- D'YES AND PROGESS MAKING THEM.- v

No Drawing.

To all whom it may concern Be it known that we, MAX HENRY Islam and OscAn BALLY, Ph. 1)., chemists, citizens of the Swiss Republic, residing at Mannheim, Germany, have invented new and useful Improvements in Anthraquinone Dyes and Processes of Making Them, of which the following is a specification.

In the specification of Patent it is stated that, by fusing benzanthrone with potassium hydrate, a .vat coloring matter can be obtained. This vat coloring matter has been termed dib'enzanthrone and possesses a constitution corresponding to the y a action product, which is obtained in-pthe formula Y 1 o have now discovered that, by treating dibenzanthrone with an oxidizing agent, we can obtain new compounds which are reducible, for instance, in aqueous suspension with sodium bisulfite or sodium sulfid or in concentrated sulfuric acid with a, reducing agent, such for instance as copper powder,

or in the presence of an organic solvent with, for lnstance, stannous chlorid. The reduced compounds can be brought back again. to the OXldlZQd'fOI'III, for instance, with an oxidizing agent. Th e new compounds, either: in the oxidized or'reduced state, dye- D cotton, from 'the hydrosulfite 'vat, olive-green shades and the-color of' the vat is blue In the! oxidized; f( rm, they give red-brown so-. 1'utionsin concentrated sulfuric midi-Whilein "the reduced form. the color of such-solu- Ytion is from violet-red to bluish fred; Our 'new com-pounds; are further characterized. by consisting when dry of dark powders:

whichare insoluble inwater, and dilute "acids.v :9. x The f ]lq 'ingexamplesgwill serve to illus trate further the. nature of our invention-and how it can be CflII'lediIltO practical effect,

Patented apt; i, row..-

but the invention is not confined to' these examples. The parts are by weight.

Example 1;: Dissolve 10 parts of puiiified dibenzanthrone, while well stirring, in 200 parts of 96% sulfuric acid, then add, slowly,

200 parts of sulfuric acid and after--- ward add, drop by'drop, at a temperatureof from about, 25 to 30 0., a solution of 7.5 parts of 62% nitric acid in 25 parts of 70% sulfuric acid. When a test portion shows that no dibenzanthrone is present,

pour the mass into Water and filter the reform of a yellowish brown paste which,

upon drying, yields a black-brown powder. 3

Its solution in concentrated sulfuric-acid is red-brown, which turns violet-red on the addition of a reducing agent, such as copper powder. It is insoluble in caustic's'oda solution, in sod um carbonate solution, and

in dilute mineral acids. It forms a blue" vat with alkaline hydrosulfite and dyes cotwhile well stirring, in 200 parts of 96% sulfuric acid and then, at a temperature of about 25 C., add a suspension of 10 parts of finely divided manganese dioxid iii. 20'

parts of96% sulfuric acid, at such'aspeed that the temperature rises of its own accord to about 60 G. Then continue stirring" for about 1 hour until a'test portion shows that no dibenzanthrone is present. Isolate the reaction product as described in the foregoing example.

If the oxidation with. manganese dioxid r v 4 be carried out in fum ng sulfuric acid, :1

soluble sulfonic acidp fthe oxidized produ t.

is obtained. a :Y'Emmple.

'B." to the ';u'spensi'onobtained by pouring filter. ,flhe'new' reduction product separates out from' the filtratein .the fo'rmfof blue H .105 ,c'e tr'atedsulfuric acid, and, upon the addiyiQIl of'water, blue flakes are obtained which are soluble wit-h a green" color in warm, yery fia s. It yields ablui'sh red'solution in con 3: oxidation. products can f be reduced,foifiinstance, .as follows: Add

Ithe melt i1 towater'as described in the-foregoing'Ex' mple l. Thenboilthetwholef and dilute caustic soda solution, so that appar-' ently a hydroxy compound of dibenzanthrone has been obtained. The hydrosulfite vat of the new product behaves in a manner similar to the vat described'in the foregoing Example 1. On oxidizing the new reduction product, for instance with manganese dioxid in the presence of sulfuric acid, the initial material, insoluble in caustic soda, is obtained.

Now what we claim is a 1. The process of producing coloring matters of the anthraquinone series by treating dibenzanthrone with an oxidizing agent.

2. The process of producing coloring matters of the anthraquinone series by treating dibenzanthrone with an oxidizing agent and then treating the product with a reducing agent.

3. The process of producing coloring matters of the anthraquinone series by treating dibenzanthrone with'nitric acid in the presence of sulfuric acid.

4. The process of producing coloring matters of the anthraquinone series by treating dibenzanthrone with nitric acid in the presence of sulfuric acid and then treatin the product so obtained with sodium bisul te.

5. As new articles of manufacture the coloring matters of the anthraquinone series which are obtainable by .treating dibenzanthrone with an oxidizing agent which consist when dry of dark powders, which are insoluble in water, and in dilute acids, which dye cotton olive-green shades, from a blue hydrosulfite vat, and which in the oxidized form give red-brown solutions in concentrated sulfuric acid and in the reduced form violet-red to bluish-red solutions.

6. As a new article of manufacture the coloring matter of the anthraquinone series which can be obtained by treating dibenzanthrone with an oxidizing agent, which coloring matter consists, when dry, of a'blaokbrown powder, which gives a red-brown solution in concentrated sulfuric acid, which solution turns violet-red on the addition of copper powder, which new coloring matter is insoluble in dilute acids and alkalis, and yields a blue vat with alkalinehydrosulfite,

and dyes cotton olive-green shades.

' In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

MAX HENRY ISLER. OSCAR BALLY.

Witnesses:

J. Ame LLoYn, JOSEPH Pnirr'nn. 

